Method For Making Catalyst Compositions Of Alkali Metal Halide-Doped Bivalent Metal Fluorides And A Process For Making Fluorinated Olefins

ABSTRACT

There is provided methods for making a catalyst composition represented by the formula MX/M′F 2  wherein MX is an alkali metal halide; M is an alkali metal ion selected from the group consisting of Li + , Na + , K + , Rb + , and Cs + ; X is a halogen ion selected from the group consisting of F − , Cl − , Br − , and I − ; M′F 2  is a bivalent metal fluoride; and M′ is a bivalent metal ion. One method has the following steps: (a) dissolving an amount of the alkali metal halide in an amount of solvent sufficient to substantially dissolve or solubilize the alkali metal halide to form an alkali metal halide solution; (b) adding an amount of the bi-valent metal fluoride to the alkali metal halide solution to form a slurry of the alkali metal halide and bi-valent metal fluoride; and (c) removing substantially all of the solvent from the slurry to form a solid mass of the alkali metal halide and bi-valent metal fluoride. Another method has the following steps: (a) adding an amount of hydroxide, oxide, or carbonate of an alkali metal to an aqueous solution of a hydrogen halide and reacted to form an aqueous solution of an alkali metal halide; (b) adding an amount of a hydroxide, oxide, or carbonate of a bivalent metal to an aqueous solution of hydrogen fluoride and reacted to form a precipitate of a bivalent metal fluoride; (c) admixing the alkali metal halide solution and the bivalent metal fluoride precipitate are admixed to form an aqueous slurry; and (d) removing water from the aqueous slurry to form a solid mass. There is also a method for making a fluorinated olefin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No.12/275,656, filed on Nov. 21, 2008, which claims priority benefit ofU.S. Provisional Application No. 61/012,566, filed on Dec. 10, 2007,each of which are incorporated herein by reference.

This application is also a Continuation-In-Part of U.S. application Ser.No. 12/167,159, filed on Jul. 2, 2008, which claims priority benefit ofU.S. Provisional Application No. 60/958,468, filed on Jul. 6, 2007, eachof which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for making catalystcompositions of alkali metal halide-doped bivalent metal fluorides. Thepresent invention also relates to a process for making fluorinatedolefins with the catalyst compositions.

2. Description of the Related Art

2,3,3,3-tetrafluoropropene (1234yf), a hydrofluoroolefin that exhibitslow global warming potential, can be used in a variety of applications,for example, as a refrigerant, a blowing agent, a solvent, a cleaningagent, and a monomer for macromolecular compounds.

One process for making 1234yf entails the dehydrochlorination of1,1,1,2-tetrafluoror-2-chloropropane (244bb). U.S. ProvisionalApplication 60/958,468, filed Jul. 6, 2007, discloses a process formaking 1234yf by dehydrochlorinating 244bb in the presence of catalystsof bivalent metal fluorides doped with alkali metal halides.

There is a need for commercially viable methods for preparing catalystsof bivalent metal fluorides doped with alkali metal halides.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a method formaking a catalyst composition. The catalyst composition is representedby the formula MX/M′F₂. MX is an alkali metal halide. M is an alkalimetal ion selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, andCs⁺. X is a halogen ion selected from the group consisting of F⁻, Cl⁻,Br⁻, and I⁻. M′F₂ is a bivalent metal fluoride. M′ is a bivalent metalion. The method has the following steps: (a) dissolving an amount of thealkali metal halide in an amount of solvent sufficient to substantiallydissolve or solubilize the alkali metal halide to form an alkali metalhalide solution; (b) adding an amount of the bi-valent metal fluoride tothe alkali metal halide solution to form a slurry of the alkali metalhalide and bi-valent metal fluoride; and (c) removing substantially allof the solvent from the slurry to form a solid mass of the alkali metalhalide and bi-valent metal fluoride.

According to the present invention, there is provided a method formaking a catalyst composition. The method has the following steps: (a)an amount of hydroxide, oxide, or carbonate of an alkali metal is addedto an aqueous solution of a hydrogen halide and reacted to form anaqueous solution of an alkali metal halide; (b) an amount of ahydroxide, oxide, or carbonate of a bivalent metal is added to anaqueous solution of hydrogen fluoride and reacted to form a precipitateof a bivalent metal fluoride therein; (c) admixing the alkali metalhalide solution and the precipitate of the bivalent metal fluoride toform an aqueous slurry; and (d) removing water from the aqueous slurryto form a solid mass.

Still further according to the present invention, there is providedprocess for making a fluorinated olefin. The process has the step ofdehydrochlorinating a hydrochlorofluorocarbon having at least onehydrogen and at least one chlorine on adjacent carbons in the presenceof a catalytically effective amount of a catalyst compositionrepresented by the formula MX/M′F₂. MX is an alkali metal halide. M isan alkali metal ion selected from the group consisting of Li⁺, Na⁺, K⁺,Rb⁺, and Cs⁺. X is a halogen ion selected from the group consisting ofF⁻, Cl⁻, Br⁻, and I⁻. M′F₂ is a bivalent metal fluoride. M′ is abivalent metal ion.

DETAILED DESCRIPTION OF THE INVENTION

Catalyst compositions that are useful products of the methods of thepresent invention are combinations/admixtures of an alkali metalhalide(s) and a bivalent metal fluoride(s) that can be represented bythe following:

MX/M′F₂

wherein MX is an alkali metal halide; M is an alkali metal ion selectedfrom the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺. X is a halogenion selected from the group consisting of F, Cl⁻, Br⁻, and I⁻. X ispreferably F⁻ and Cl⁻. M′F₂ is a bivalent metal fluoride. M′ is abivalent metal ion. M′ is preferably selected from the group consistingof Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ni²⁺, Fe²⁺, Co²⁺, Cu²⁺, and Zn²⁺. M′ is mostpreferably Mg²⁺.

The catalyst compositions can alternately be represented by thefollowing:

n % MX/M′F₂

wherein n % is the weight percentage of alkali metal halide in thecomposition based upon the total weight of the composition. The alkalimetal halide is preferably from about 0.05 wt % to about 50 wt %, morepreferably about 5 wt % to about 15 wt %, and most preferably about 7.5wt % to about 12.5 wt % of the catalyst composition based on the totalweight of the catalyst composition.

Examples of alkali metal halides include LiCl, NaCl, KCl, RbCl, CsCl,LiF, NaF, KF, RbF, and CsF. Preferred alkali metal halides include KCl,CsCl, KF, and CsF. Examples of bi-valent metal fluorides include Mg F₂,CaF₂, SrF₂, BaF₂, NiF₂, FeF₂, Co F₂, CuF₂, and ZnF₂. Preferred bi-valentmetal fluorides include MgF₂ and NiF₂.

The alkali metal halide is added to an amount of solvent sufficient tosubstantially dissolve or solubilize the alkali metal halide. Thepreferred solvent is one in which the alkali metal halide is readilysoluble. The choice of solvent may vary depending on the particularalkali metal halide(s). Examples of solvents that can be used for thepreparation of the catalyst compositions of the present inventioninclude water, alcohols, ethers, and mixtures thereof. Useful alcoholsinclude monohydric and polyhydric alcohols. Most preferred alcohols arethose that are monohydric and have 1 to 5 carbon atoms. A most preferredsolvent is water.

In one embodiment of the method of the invention, the bi-valent metalfluoride is added to the solution of the alkali metal halide to form aslurry. After formation of the slurry, substantially all of the solventis removed to form a solid mass of a mixture of the alkali metal halideand bi-valent metal fluoride. Although the solvent can be removed in onestep, a preferred method is to drive off a portion of the solvent fromthe slurry to form a paste and then follow by drying the paste to formthe solid mass. Any conventional technique can be used to drive off thesolvent. Examples of such techniques include vigorous stirring at roomor elevated temperatures, evaporation, settling and decanting,centrifugation, and filtration. It is preferred to evaporate off adesired amount of solvent to form the paste. The paste is then dried byany suitable method to form a free-flowing, substantially solvent-freepowder. Preferred methods for drying include oven drying, mostpreferably at temperatures from about 110° C. to about 120° C., andspray drying. Being solvent free means that less than 1 wt. %,preferably about 0.5 wt % or less, more preferably about 0.1 wt % orless, and most preferably no solvent will remain with the powder aftersolvent removal/drying. Upon removal of solvent, the powder will takethe form of a solid mass (or powder) of a mixture of particles of thealkali metal halide and the bi-valent metal fluoride.

In another embodiment of the method of the present invention, a slurryof the alkali metal halide and the bivalent metal fluoride is preparedby a different, reactive technique. In a first step, a hydroxide, oxide,or carbonate of an alkali metal is added to an aqueous solution of ahydrogen halide and reacted to form an aqueous solution of an alkalimetal halide. In a second step, a hydroxide, oxide, or carbonate of abivalent metal is added to an aqueous solution of hydrogen fluoride andreacted to form a precipitate of a bivalent metal fluoride therein. In athird step, the alkali metal halide solution and the bivalent metalfluoride precipitate are then admixed to form an aqueous slurry. In afourth step, water is then removed from the aqueous slurry in the mannerdescribed herein to form a solid mass.

Optionally, the solid mass of the mixture of the alkali metal halide andthe bi-valent metal fluoride powder is then calcined. Calcination ispreferably carried out at a temperature of about 100° C. to about 750°C., more preferably at a temperature of about 200° C. to about 600° C.,and most preferably at a temperature of about 300° C. to about 600° C.Calcination may further optionally be carried out in the presence of aninert gas, such as nitrogen or argon.

After calcination, the powder is optionally further grinded such that itbecomes more finely-divided. The powder is further optionally pelletizedin order to form pellets. The pellets then provide catalyst surfaces touse in actual process application.

The catalyst compositions of the present invention may affordperformance advantages over compositions that are obtained by simple drymixing of components. A more complete degree of intermixing may beachieved. The complete degree of mixing may manifest itself in higherselectivity to the target product, such as 1234yf (and less to theformation of a dehydrofluorinating product, such as 1233xf).

The catalyst compositions are useful in convertinghydrochlorofluorocarbons to fluorinated olefins. Usefulhydrochlorofluorocarbons have at least one hydrogen and at least onechlorine on adjacent carbons.

Table 1 sets forth examples of fluorinated olefins and precursorhydrochlorofluorocarbons from which they can be obtained (precursorhydrochlorofluorocarbon in left column and corresponding productfluorinated olefin in the right column).

TABLE 1 Hydrochlorofluorocarbon Fluorinated Olefin(s)chlorotetrafluoropropane tetrafluoropropene chloropentafluoropropanepentafluoropropene chlorohexafluoropropane hexafluoropropene1,1,1,2-tetrafluoro-2-chloropropane 2,3,3,3-tetrafluoropropeneCF₃CFClCH₃ (244bb) CF₃CF═CH₂ (1234yf)1,1,1,2-tetrafluoro-3-chloropropane 2,3,3,3-tetrafluoropropeneCF₃CHFCH₂Cl (244eb) CF₃CF═CH₂ (1234yf)1,1,1,3-tetrafluoro-3-chloropropane 1,3,3,3-tetrafluoropropeneCF₃CH₂CHFCl (244fa) CF₃CH═CHF (trans/cis-1234ze)1,1,1,3-tetrafluoro-2-chloropropane 1,3,3,3-tetrafluoropropeneCF₃CHClCH₂F (244db) CF₃CH═CHF (trans/cis-1234ze)1,1,1,2,3-pentafluoro-2-chloropropane 1,2,3,3,3-pentafluoropropeneCF₃CFClCH₂F (235bb) CF₃CF═CHF (Z/E-1225ye)1,1,1,2,3-pentafluoro-3-chloropropane 1,2,3,3,3-pentafluoropropeneCF₃CHFCHFCl (235ea) CF₃CF═CHF (Z/E-1225ye)1,1,1,3,3-pentafluoro-3-chloropropane 1,1,3,3,3-pentafluoropropeneCF₃CH₂CF₂Cl (235fa) CF₃CH═CF₂ (1225zc)1,1,1,3,3-pentafluoro-2-chloropropane 1,1,3,3,3-pentafluoropropeneCF₃CHClCHF₂ (235da) CF₃CH═CF₂ (1225zc)1,1,1,2,3,3-hexafluoro-2-chloropropane 1,1,2,3,3,3-hexafluoropropeneCF₃CFClCHF₂ (226ba) CF₃CF═CF₂ (1216)1,1,1,2,3,3-hexafluoro-3-chloropropane 1,1,2,3,3,3-hexafluoropropeneCF₃CHFCF₂Cl (226ea) CF₃CF═CF₂ (1216)

The following are examples of the invention and are not to be construedas limiting.

EXAMPLES

In the following examples, 244bb is dehydrochlorinated to 1234yf in thepresence of the catalysts of combinations of alkali metal halides andbivalent metal fluorides.

Example 1 244bb Dehydrohalogenation Over CsCl/MgF₂ Catalysts HavingVarious CsCl Loadings

A series of CsCl/MgF₂ catalysts with various loadings of CsCl weretested to determine the effect of CsCl loading on reactivity. 20 cc ofcatalyst pellets was typically used. A mixture of 97.2%/2.0%244bb/1233xf was passed through catalyst bed at a rate of 6 g/h(grams/hour) at a temperature ranging from 470° C. to 520° C. Thetemperatures at the bottom and top of the catalyst bed were measured. Asshown in Table 2 below, activity remained at about the same levelregardless of loading, while the selectivity to 1233xf (a non-desireddehydrofluorination product) decreased as CsCl loading increased to 5.0wt %. No 1233xf was formed over the 10 wt % CsCl/MgF₂ catalyst.

TABLE 2 (Effect of CsCl loading on the performance of CsCl/MgF₂catalysts during 244bb dehydrohalogenation*) Temp. Con- CsCl Bottom-version, Selectivity Selectivity Selectivity loading Top time (%) (%)(%) (%) (wt %) (°) (h) 244bb 1234yf 1233xf others 0.0 475-506 1 48.276.9 17.7 5.4 475-509 2 52.9 79.8 14.6 5.6 475-509 3 53.3 80.7 12.9 6.4475-507 4 52.4 81.4 11.9 6.7 475-509 5 54.2 83.0 10.9 6.1 475-510 6 54.183.6 10.2 6.2 475-508 7 54.7 84.7 9.6 5.7 475-509 8 53.7 85.4 9.2 5.4475-510 9 54.9 86.0 8.6 5.5 475-509 10 53.5 86.7 8.2 5.1 2.5 500-514 148.4 88.7 5.2 6.1 500-514 2 48.1 88.5 5.2 6.3 500-514 3 49.5 89.1 5.05.9 500-507 4 46.9 89.3 4.8 5.9 500-509 5 48.5 89.9 4.6 5.5 500-513 648.5 89.6 4.7 5.7 500-514 7 49.6 89.9 4.6 5.5 5.0 490-510 1 49.0 94.80.5 4.7 490-511 2 51.0 94.5 0.4 5.1 490-510 3 49.2 95.3 0.5 4.2 490-5054 48.7 95.0 0.4 4.6 490-507 6 49.8 95.4 0.4 4.2 490-503 8 49.2 95.7 0.43.9 10.0  475-511 1 49.6 96.9 3.1 475-510 2 51.2 97.0 3.0 475-511 3 51.896.9 3.1 475-508 4 50.4 96.9 3.1 475-510 5 51.4 97.0 3.0 •Reactionconditions: 20 ml of catalyst, 6 grams organic/hour, 97.2% 244bb/2.0%1233xf, 1 atm pressure

Example 2 244bb Dehydrohalogenation Over 10 wt % Alkali MetalChloride/MgF₂ Catalysts

10 wt % KCl/MgF₂ and 10 wt % CsCl/MgF₂ catalysts were tested. 20 cc ofcatalyst pellets was used. A mixture of 99.1%/0.4% 244bb/1233xf waspassed through the catalyst bed at a rate of 6 g/h at a temperatureranging from 380° C. to 480° C. The temperature at the bottom and top ofthe catalyst bed were measured. As shown in Table 2, both catalystsexhibited about the same activity (20%), while the 10 wt % CsCl/MgF₂catalyst provided a higher selectivity to 1234yf without generation of1233xf over the catalyst.

TABLE 3 (Reactivity of 10 wt % KCl/MgF₂ and 10 wt % CsCl/MgF₂ Catalystsduring 244bb Dehydrohalogenation*) Temp. Con- Bottom- versionSelectivity Selectivity Selectivity Top time (%) (%) (%) (%) Catalyst(°) (hour) 244bb 1234yf 1233xf others 10 wt % 405-477 1 21.9 89.1 0.410.5 KCl/MgF₂ 405-480 2 17.8 95.2 0.6 4.2 405-480 4 20.0 95.8 0.6 3.6405-480 6 21.2 96.0 0.6 3.7 405-480 8 20.1 96.1 0.6 3.3 405-480 10 21.596.2 0.6 3.1 405-480 12 20.9 96.2 0.6 3.2 405-479 14 20.5 96.3 0.6 3.1405-479 16 20.2 96.2 0.6 3.2 405-479 18 20.1 96.3 0.6 3.1 405-480 2020.5 96.4 0.6 3.0 405-478 22 20.4 96.4 0.6 3.0 405-478 24 19.9 96.3 0.63.1 10 wt % 380-481 1 10.3 91.1 0.0 8.9 CsCl/MgF₂ 380-481 2 14.0 95.90.0 4.1 380-482 4 16.8 96.7 0.0 3.3 380-484 6 19.6 97.4 0.0 2.6 380-4828 20.0 97.5 0.0 2.5 380-481 10 20.5 97.5 0.0 2.5 380-481 12 20.6 97.80.0 2.2 380-479 14 19.9 97.7 0.0 2.3 380-478 16 20.0 97.8 0.0 2.2380-481 18 21.0 97.8 0.0 2.2 380-483 20 21.8 98.0 0.0 2.0 380-481 2220.7 97.7 0.0 2.3 380-481 24 19.7 97.6 0.0 2.4 •Reaction conditions: 20ml of catalyst, 6 grams organic/hour, 99.1%/0.4% 244bb/1233xf, 1 atmpressure

Example 3 244bb Dehydrohalogenation Over 10 wt % CsCl/Bi-Valent MetalFluoride Catalysts

10 wt % CsCl/NiF₂ and 10 wt % CsCl/MgF₂ catalysts were tested. 20 cc ofcatalyst pellets was used. A mixture of 99.1%/0.4% 244bb/1233xf waspassed through a catalyst bed at a rate of 6 g/h at a temperatureranging from 380° C. to 480° C. The temperature at the bottom and top ofthe catalyst bed were measured. As shown in Table 4, both catalystsexhibited about the same selectivity to 1234yf (97% to 98%), while the10 wt % CsCl/MgF₂ catalyst provided higher activity.

TABLE 4 (Reactivity of MgF₂ and Alkaline Metal Chloride-Doped MgF₂Catalysts during 244bb Dehydrohalogenation*) Temp. Con- Bottom- versionSelectivity Selectivity Selectivity Top time (%) (%) (%) (%) Catalyst(°) (hour) 244bb 1234yf 1233xf others 10 wt % 410-482 1 5.6 86.3 0.013.7 CsCl/NiF₂ 410-482 2 8.3 90.4 0.0 9.6 410-483 4 9.9 93.6 0.0 6.4410-480 6 10.1 95.2 0.0 4.8 410-481 8 10.9 95.9 0.0 4.1 410-480 10 12.096.2 0.0 3.8 410-481 12 13.2 96.8 0.0 3.2 410-482 14 14.2 97.1 0.0 2.9410-481 16 14.4 97.3 0.0 2.7 410-481 18 14.7 97.3 0.0 2.7 410-480 2014.8 97.4 0.0 2.6 410-481 22 15.1 97.8 0.0 2.2 410-480 24 15.4 97.6 0.02.4 10 wt % 380-481 1 10.3 91.1 0.0 8.9 CsCl/MgF₂ 380-481 2 14.0 95.90.0 4.1 380-482 4 16.8 96.7 0.0 3.3 380-484 6 19.6 97.4 0.0 2.6 380-4828 20.0 97.5 0.0 2.5 380-481 10 20.5 97.5 0.0 2.5 380-481 12 20.6 97.80.0 2.2 380-479 14 19.9 97.7 0.0 2.3 380-478 16 20.0 97.8 0.0 2.2380-481 18 21.0 97.8 0.0 2.2 380-483 20 21.8 98.0 0.0 2.0 380-481 2220.7 97.7 0.0 2.3 380-481 24 19.7 97.6 0.0 2.4 •Reaction conditions: 20ml of catalyst, 6 grams organic/hour, 99.1% 244bb/0.4% 1233xf, 1 atmpressure

Example 4 244bb Dehydrohalogenation Over Alkaline Metal Chloride-DopedMgF₂ Catalysts

In Example 4, a series of alkaline metal chlorides were investigated asan additive to MgF₂ with a purpose of improving the selectivity to1234yf. For comparison purpose, the results obtained over MgF₂ catalystwere also reported. 20 cc of catalyst pellets was used in a typical run.A mixture of 97.2% 244bb/2.0% 1233xf was passed through catalyst bed ata rate of 6 g/h (grams/hour) at a temperature ranged from 470° C. to520° C. The temperatures at the bottom of catalyst bed and at the top ofcatalyst bed were measured.

As shown in Table 5, the MgF₂ provided a 244bb conversion of 53-55%, a1234yf selectivity of 80-87%, and a 1233xf selectivity of 8-15%; the 10%LiCl/MgF₂ provided a 244bb conversion below 45%, a 1234yf selectivity ofabout 90%, and a 1233xf selectivity of about 5%; the 10% KCl/MgF₂provided a 244bb conversion below 50%, a 1234yf selectivity of about96%, and a 1233xf selectivity of about 1%; and the 10% CsCl/MgF₂provided a 244bb conversion of 50-52%, a 1234yf selectivity of about97%, and no formation of 1233xf. CsCl exhibited the best results. The10% CsCl/MgF₂ catalyst provided activity comparable to MgF₂ and thehighest 1234yf selectivity while generating no 1233xf.

TABLE 5 (Reactivity of alkaline metal chloride-doped MgF₂ catalystsduring 244bb dehydrohalogenation*) Temp. Con- Bottom- versionSelectivity Selectivity Selectivity, Top t 244bb 1234yf 1233xf UnknownsCatalyst (°) (h) (%) (%) (%) (%) 10 wt % 475-490 1 29.4 89.1 5.3 5.6LiCl/MgF₂ 475-506 2 38.8 89.6 5.3 5.0 475-505 3 40.4 89.9 5.2 4.9475-507 4 42.9 90.5 4.8 4.7 10 wt % 475-514 1 38.3 95.1 0.9 4.0 KCl/MgF₂475-515 3 47.2 95.6 0.8 3.6 475-515 5 47.5 95.8 0.7 3.5 475-509 6 43.795.8 0.6 3.5 475-514 7 47.1 95.8 0.7 3.5 10 wt % 475-511 1 49.6 96.9 3.1CsCl/MgF₂ 475-510 2 51.2 97.0 3.0 475-511 3 51.8 96.9 3.1 475-508 4 50.496.9 3.1 475-510 5 51.4 97.0 3.0 •Reaction conditions: 20 ml ofcatalyst, 6 grams-organic/hour, 97.2% 244bb/2.0% 1233xf, pressure = 1atm

Additional teachings to catalyst compositions havingmixtures/combinations of alkali metal halides and bivalent metalfluorides and use of same in dehydrochlorinating hydrofluorocarbons tofluorinated olefins is shown in U.S. Provisional Patent Application No.60/958,468, filed Jul. 6, 2007, which is incorporated herein byreference.

It should be understood that the foregoing description is onlyillustrative of the present invention. Various alternatives andmodifications can be devised by those skilled in the art withoutdeparting from the invention. Accordingly, the present invention isintended to embrace all such alternatives, modifications and variancesthat fall within the scope of the appended claims.

1.-30. (canceled)
 31. A process for making a fluorinated olefin,comprising: dehydrochlorinating a hydrochlorofluorocarbon having atleast one hydrogen and at least one chlorine on adjacent carbons in thepresence of a catalytically effective amount of a catalyst compositionrepresented by the following:MX/M′F₂ wherein MX is an alkali metal halide; M is an alkali metal ionselected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺; X is ahalogen ion selected from the group consisting of F⁻, Cl⁻, Br⁻, and I⁻;M′F₂ is a bivalent metal fluoride; and M′ is a bivalent metal ion. 32.The process of claim 31, wherein the hydrochlorofluorocarbon and thefluorinated olefin are each selected from the groups consisting of thefollowing: Hydrochlorofluorocarbon Fluorinated olefinchlorotetrafluoropropane tetrafluoropropene chloropentafluoropropanepentafluoropropene chlorohexafluoropropane hexafluoropropene1,1,1,2-tetrafluoro-2-chloropropane 2,3,3,3-tetrafluoropropeneCF₃CFClCH₃ (244bb) CF₃CF═CH₂ (1234yf)1,1,1,2-tetrafluoro-3-chloropropane 2,3,3,3-tetrafluoropropeneCF₃CHFCH₂Cl (244eb) CF₃CF═CH₂ (1234yf)1,1,1,3-tetrafluoro-3-chloropropane 1,3,3,3-tetrafluoropropeneCF₃CH₂CHFCl (244fa) CF₃CH═CHF (trans/cis-1234ze)1,1,1,3-tetrafluoro-2-chloropropane 1,3,3,3-tetrafluoropropeneCF₃CHClCH₂F (244db) CF₃CH═CHF (trans/cis-1234ze)1,1,1,2,3-pentafluoro-2-chloropropane 1,2,3,3,3-pentafluoropropeneCF₃CFClCH₂F (235bb) CF₃CF═CHF (Z/E-1225ye)1,1,1,2,3-pentafluoro-3-chloropropane 1,2,3,3,3-pentafluoropropeneCF₃CHFCHFCl (235ea) CF₃CF═CHF (Z/E-1225ye)1,1,1,3,3-pentafluoro-3-chloropropane 1,1,3,3,3-pentafluoropropeneCF₃CH₂CF₂Cl (235fa) CF₃CH═CF₂ (1225zc)1,1,1,3,3-pentafluoro-2-chloropropane 1,1,3,3,3-pentafluoropropeneCF₃CHClCHF₂ (235da) CF₃CH═CF₂ (1225zc)1,1,1,2,3,3-hexafluoro-2-chloropropane 1,1,2,3,3,3-hexafluoropropeneCF₃CFClCHF₂ (226ba) CF₃CF═CF₂ (1216)1,1,1,2,3,3-hexafluoro-3-chloropropane 1,1,2,3,3,3-hexafluoropropeneCF₃CHFCF₂Cl (226ea) CF₃CF═CF₂ (1216)


33. The method of claim 31, wherein M′ is selected from the groupconsisting of Mg²⁺, Ca²⁺, Sr⁺, Ba²⁺, Ni²⁺, Fe²⁺, Co²⁺, Cu²⁺, and Zn²⁺.34. The method of claim 31, wherein the alkali metal halide is fromabout 0.05 wt % to about 50 wt % of the catalyst composition based onthe total weight of the catalyst composition.
 35. The method of claim34, wherein the alkali metal halide is from about 5 wt % to about 15 wt% of the catalyst composition based on the total weight of the catalystcomposition.
 36. The method of claim 35, wherein the alkali metal halideis from about 7.5 wt % to about 12.5 wt % of the catalyst compositionbased on the total weight of the catalyst composition.
 37. The method ofclaim 31, wherein M is selected from the group consisting of potassiumand cesium, wherein X is selected from the group consisting of F⁻ andCl⁻, and wherein M′ is selected from the group consisting of Mg²⁺ andNi²⁺.
 38. The method of claim 37, wherein M is cesium, X is Cl⁻ or F⁻and M′ is Mg²⁺.